CN111893257B - Cold-rolled steel wire having high fatigue strength and hydrogen embrittlement resistance and reinforced flexible pipe incorporating the same - Google Patents
Cold-rolled steel wire having high fatigue strength and hydrogen embrittlement resistance and reinforced flexible pipe incorporating the same Download PDFInfo
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- CN111893257B CN111893257B CN202010637964.2A CN202010637964A CN111893257B CN 111893257 B CN111893257 B CN 111893257B CN 202010637964 A CN202010637964 A CN 202010637964A CN 111893257 B CN111893257 B CN 111893257B
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- 239000010960 cold rolled steel Substances 0.000 title claims abstract description 13
- 229910052739 hydrogen Inorganic materials 0.000 title abstract description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title abstract description 10
- 239000001257 hydrogen Substances 0.000 title abstract description 10
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 20
- 239000010959 steel Substances 0.000 claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 claims abstract description 19
- 229910001563 bainite Inorganic materials 0.000 claims abstract description 14
- 229910000859 α-Fe Inorganic materials 0.000 claims abstract description 14
- 229910001562 pearlite Inorganic materials 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 5
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 4
- 239000012535 impurity Substances 0.000 claims abstract description 3
- 229910052742 iron Inorganic materials 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims description 20
- 238000001816 cooling Methods 0.000 claims description 13
- 230000009466 transformation Effects 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 7
- 238000005097 cold rolling Methods 0.000 claims description 6
- 229910000734 martensite Inorganic materials 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000005279 austempering Methods 0.000 claims description 4
- 238000005452 bending Methods 0.000 claims description 4
- 238000005482 strain hardening Methods 0.000 claims description 4
- 230000006698 induction Effects 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims description 2
- 238000010791 quenching Methods 0.000 claims description 2
- 230000000171 quenching effect Effects 0.000 claims description 2
- 238000012360 testing method Methods 0.000 description 7
- 239000011651 chromium Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 230000002411 adverse Effects 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- AZFNGPAYDKGCRB-XCPIVNJJSA-M [(1s,2s)-2-amino-1,2-diphenylethyl]-(4-methylphenyl)sulfonylazanide;chlororuthenium(1+);1-methyl-4-propan-2-ylbenzene Chemical compound [Ru+]Cl.CC(C)C1=CC=C(C)C=C1.C1=CC(C)=CC=C1S(=O)(=O)[N-][C@@H](C=1C=CC=CC=1)[C@@H](N)C1=CC=CC=C1 AZFNGPAYDKGCRB-XCPIVNJJSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 235000010289 potassium nitrite Nutrition 0.000 description 1
- 239000004304 potassium nitrite Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Substances [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/52—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for wires; for strips ; for rods of unlimited length
- C21D9/525—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for wires; for strips ; for rods of unlimited length for wire, for rods
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- C—CHEMISTRY; METALLURGY
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- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/06—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of rods or wires
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
- B21C1/00—Manufacture of metal sheets, metal wire, metal rods, metal tubes by drawing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21F—WORKING OR PROCESSING OF METAL WIRE
- B21F1/00—Bending wire other than coiling; Straightening wire
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- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/18—Hardening; Quenching with or without subsequent tempering
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- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/18—Hardening; Quenching with or without subsequent tempering
- C21D1/19—Hardening; Quenching with or without subsequent tempering by interrupted quenching
- C21D1/20—Isothermal quenching, e.g. bainitic hardening
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- C21D1/26—Methods of annealing
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- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
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- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/34—Methods of heating
- C21D1/42—Induction heating
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- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
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- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/56—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering characterised by the quenching agents
- C21D1/607—Molten salts
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- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/06—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of rods or wires
- C21D8/065—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of rods or wires of ferrous alloys
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- C21D9/0006—Details, accessories not peculiar to any of the following furnaces
- C21D9/0018—Details, accessories not peculiar to any of the following furnaces for charging, discharging or manipulation of charge
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- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/52—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for wires; for strips ; for rods of unlimited length
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C38/00—Ferrous alloys, e.g. steel alloys
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- C22C38/001—Ferrous alloys, e.g. steel alloys containing N
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
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- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
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- C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
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- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
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- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/22—Ferrous alloys, e.g. steel alloys containing chromium with molybdenum or tungsten
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- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
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- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
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- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B17/00—Drilling rods or pipes; Flexible drill strings; Kellies; Drill collars; Sucker rods; Cables; Casings; Tubings
- E21B17/01—Risers
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- C21D2211/00—Microstructure comprising significant phases
- C21D2211/009—Pearlite
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Abstract
The invention relates to a cold-rolled steel wire having high fatigue strength and hydrogen embrittlement resistance, and a reinforced flexible pipe incorporating the same, the steel having the following chemical composition, expressed in weight percentages: 0.2. ltoreq. C.ltoreq.0.6, 0.5. ltoreq. Mn.ltoreq.1.0, 0.1. ltoreq. Si.ltoreq.0.5, 0.2. ltoreq. Cr.ltoreq.1.0, P.ltoreq.0.020, S.ltoreq.0.015, N.ltoreq.0.010, and optionally not more than 0.07% of Al, not more than 0.2% of Ni, not more than 0.1% of Mo and not more than 0.1% of Cu, the balance being iron and unavoidable impurities resulting from production. The wire has a microstructure comprising bainite and optionally up to 35% acicular ferrite and up to 15% pearlite. The invention also relates to a production method and to a flexible pipe incorporating said filaments for the production of hydrocarbons.
Description
This application is a divisional application of the chinese patent application entitled "cold-rolled steel wire with high fatigue strength and hydrogen embrittlement resistance and reinforced flexible pipe incorporating the same", application No. 201480070438.5, patent application 201480070438.5 is a national application entering the chinese national phase according to the international application (PCT/FR2014/000301) filed about 12/22/2014 in patent cooperation treaty.
Technical Field
The invention relates to the field of metallurgy applied to offshore oil production. It relates in particular to steel wires which can be used as reinforcing or structural elements for submerged structures or assemblies such as flexible offshore pipelines, whether for transporting liquid or gaseous hydrocarbons.
Background
It is known that the basic requirements regarding such filaments, besides good mechanical characteristics, are also the presence of H in sulphur (in particular present in transported fluids and hydrocarbons)2Form of S) in an acidic environment.
Steel wires for offshore use, which are commercially available at present, are mainly made of low-alloy grades with a tensile strength Rm of about 800 MPa.
In order to produce these cold-rolled wires in a known manner, manganese steels are used which contain from 0.15 to 0.80% by weight of carbon and whose initial microstructure is ferrite-pearlite. After shaping the initial round rolled wire rod, a suitable stress relief heat treatment is applied to obtain the desired hardness. However, due to the strong presence of H in the transported hydrocarbons2S, the cold rolled wire obtained by these conventional methods cannot withstand the relatively strong acidity encountered in deep water.
Furthermore, flexible offshore pipelines must at present be suitable for use at increasingly greater underwater depths, which requires an increase in mechanical breaking strength beyond 800MPa, as well as an increase in making them resistant to the presence of H2S and CO2Corrosion fatigue strength of the resulting corrosion.
Furthermore, the market constraints with respect to price are becoming more and more tight, which has an adverse effect on the customary or prolonged or large-scale use of precious alloying elements (such as chromium, niobium, etc. and their expensive processing steps, especially if they have to be carried out under hot conditions).
Disclosure of Invention
It is therefore an object of the present invention to make available a solution in an acid environment (H)2S type acidic environment) and very good hydrogen embrittlement resistance and very good corrosion fatigue strength properties (CO)2+H2S) to meet new constraints in the oil and gas market, in particular by using low alloy steel compositions.
More particularly, the object is to use a catalyst containing 5mbar of H2S or more H2S (hydrogen embrittlement resistance) environment there were no internal cracks after 30 days of testing under stress at pH 4.1.
Another object is to provide a catalyst containing H2S and CO2Under an alternating stress of +100MPa to +600MPa there is no fatigue failure (fatigue fracture) after two million bending cycles. Even more particularly and preferably, the objective is that there is no fatigue failure (corrosion fatigue strength) even for up to four million cycles.
In addition to these use characteristics of the wire, another object is excellent mechanical characteristics, and in particular a mechanical breaking strength of 800MPa to 1300MPa and a ductility a of greater than or equal to 10% to facilitate the forming operation.
The object of the invention is a filament as described in claim 1. The filaments may also have the features recited in claims 2 to 5, considered individually or in combination.
Another object of the invention is a method as described in claim 6. The method may also comprise the features recited in claims 7 to 11 considered individually or in combination.
Another object of the invention is a pipe as claimed in claim 12.
According to the invention, the steel grade (grade) used for the wire according to the invention comprises the following elements, expressed in weight percent:
0.2≤C%≤0.6
0.5≤Mn%≤1.0
0.1≤Si≤0.5%
0.2≤Cr≤1.0%
P≤0.020%
S≤0.015%
N≤0.010%
and optionally not more than 0.07% Al, not more than 0.2% Ni, not more than 0.1% Mo and not more than 0.1% Cu.
The carbon content is 0.2 to 0.6 wt.%. Said low value makes it possible to ensure that a sufficient hardness is obtained after the heat treatment. The maximum content is limited to 0.6% to sufficiently protect ductility necessary for cold forming during manufacturing of the wire.
The manganese content is 0.5 to 1.0 wt.%. Said low values make it possible to ensure that the desired majority bainite microstructure is obtained. The maximum content is limited to 1.0% to prevent the formation of relatively undeformed phases (such as martensite).
The silicon content is 0.1 to 0.5 wt.%. Said low value combined with a low chromium level makes it possible to ensure that the microstructure specified according to the invention is obtained in the entire cross-section of the shaped wire. The maximum content is limited to 0.5% in order here again to prevent the formation of martensite during the heat treatment, since this phase is then not deformable.
The chromium content is from 0.2 to 1.0% by weight. Said low value in combination with a low level of silicon makes it possible to ensure that the microstructure specified according to the invention is obtained in the entire cross section of the shaped wire. The maximum content is limited to 1.0% to prevent the formation of martensite during heat treatment.
The phosphorus content is limited to 0.020 wt% to limit segregation, which adversely affects hydrogen embrittlement and fatigue resistance.
The sulfur content is limited to 0.015 wt% to limit the presence of inclusions, which adversely affect fatigue performance and hydrogen embrittlement.
The nitrogen content is limited to 0.010 wt% to limit the presence of nitrides, which adversely affect fatigue performance.
The steel grade may also contain up to 0.07% Al, up to 0.2% Ni, up to 0.1% Mo and up to 0.1% Cu. The presence of these elements is limited because they cause diffusion behavior during heat treatment.
Another essential element of the wire according to the invention is that the microstructure of the steel from which the wire is made comprises bainite. It may also contain acicular ferrite up to 35% by area percentage. Generally lamellar pearlite can also be present in an area percentage of up to 15%, preferably up to 10%, and more particularly preferably not at all in the microstructure, as its presence is not desired.
Thus, the desired microstructure may be bainite or bainite-ferrite, the area percentage of the sum of the bainite and acicular ferrite phases being preferably greater than 50%, preferably greater than 70%, most particularly preferably greater than 90%, or even equal to 100% of the area.
In addition to the proportionally limited pearlite, it is also desirable to avoid the presence of martensite, which would make it impossible to manufacture the wire according to the invention.
The cold rolled wire (sometimes referred to as formed wire) according to the present invention may exhibit any cross section suitable for its final application. In particular, it may have a regular circular cross-section, which is usually obtained, for example, by simple drawing from a larger diameter wire rod.
It may also have a cross section that is rectangular or flat or U-shaped, Z-shaped, T-shaped, etc., which typically requires a combination of drawing and rolling operations. These latter cross-sections of more complex shape will allow the filaments to fit or fasten together at the edges to each other to form a hinged support bundle.
It is more particularly intended for offshore production operations to constitute reinforcing wires, lashing wires or archwires (arch wires) into pipelines and other flexible pipe structures. The cold rolled steel wire is looped in a so-called "loop" region in the pipe between two layers of extruded polymer.
The filaments according to the invention may be manufactured by any suitable method that makes it possible to obtain the desired characteristics of use. However, it is preferred to use a method according to the invention, which comprises the following steps:
-obtaining a hot-rolled steel wire rod having a diameter greater than or equal to 10mm,
-subjecting the wire rod to an austenitizing heat treatment at a temperature greater than 950 ℃ and then
-cooling the wire rod by austempering to a temperature of 350 ℃ to 600 ℃ to obtain a structure comprising at least 50% bainite and optionally up to 35% acicular ferrite and up to 15% pearlite, followed by completion of cooling to room temperature at a cooling rate of 30 ℃/s to 100 ℃/s,
-subjecting the cooled wire rod to a cold mechanical transformation operation with a total work hardening rate of 40% to 90% to obtain a mechanical tensile strength Rm of at least 800MPa, and then
-subjecting it to an optional stress relief heat treatment.
The method according to the invention may also comprise the following features considered alone or in combination:
the austenitizing heat treatment to which the wire rod is subjected is carried out continuously on the previously unwound wire, preferably in a gas furnace or in an induction furnace,
-the austenitizing heat treatment is carried out for a time ranging from 2 minutes to 10 minutes,
-the wire rod is cooled by austempering, preferably for a time of from 1 to 10 minutes, in a molten bath preferably based on lead or salt groups (a mixture of nitric acid/sodium or potassium nitrite), or in a fluidized bed of said same elements, preferably followed by water cooling,
-the cold mechanical transformation operation comprises a drawing step followed by a cold rolling step, said drawing preferably being carried out so as to obtain a reduction in cross section of at least 15% or even 20%, and said cold rolling preferably being carried out so as to obtain a reduction in thickness of at least 30%,
-performing said cold mechanical transformation operation to obtain a mechanical tensile strength Rm of at least 1000MPa, and subsequently performing a stress relief heat treatment so that the mechanical tensile strength Rm does not decrease below 800MPa, or even below 850MPa or 900 MPa.
Furthermore, the stress relief operation makes it possible to improve the hydrogen embrittlement resistance of the wire.
Drawings
Figure 1 is a microscopic image showing the different components (bainite, acicular ferrite and lamellar pearlite) of the microstructure obtained with steel grade 1;
fig. 2 is a microscopic image showing the different components of the microstructure obtained with steel grade 3.
Detailed Description
For a better explanation of the invention, some tests were performed, but these tests are for illustrative purposes only and are not intended to be limiting.
Testing
Tests carried out to evaluate the performance of the filaments according to the invention were carried out under the following conditions:
hydrogen embrittlement (HIC)&SSCC test-NACE TM0177 and NACE TM0284 standards)
Immersing the steel wire in an aqueous solution having a pH of 4.1 under a stress of 650MPa to contain CO2And 5mbar H2A gas of S is bubbled through the aqueous solution. The test was carried out for more than 30 days, at the end of which the filaments were examined using ultrasound to check for possible internal cracks.
Fatigue strength in corrosive environments
Immersing the steel wire in an aqueous solution having a pH of 5 under an alternating bending stress of 100MPa to 500MPa to contain CO2And up to 5mbar of H2A gas of S is bubbled through the aqueous solution. The test was stopped when the wire broke and the number of million cycles reached was recorded.
First a series of steel grades was prepared, the chemical composition of which is listed in table 1 in weight percent:
TABLE 1
C | Mn | Si | Cr | P | S | N | Al | Ni | Mo | Cu | |
1 | 0.360 | 0.680 | 0.210 | 0.250 | 0.010 | 0.011 | 0.007 | 0.045 | 0.050 | 0.010 | 0.050 |
2 | 0.340 | 0.700 | 0.180 | 0.350 | 0.011 | 0.008 | 0.006 | 0.043 | 0.060 | 0.015 | 0.060 |
3 | 0.320 | 0.725 | 0.180 | 0.406 | 0.011 | 0.010 | 0.003 | 0.020 | 0.020 | 0.015 | 0.009 |
Then, for steel grades 1 to 3, hot-rolled round wire rods having a diameter of 15mm were conventionally manufactured and wound on bobbins. Then, in a second step, the previously unwound wire is austenitized in a gas furnace at 1000 ℃ for 6 minutes.
Steel grades 1 and 2 were then austempered in a molten lead bath at 500 ℃ and steel grade 3 at 410 ℃ for 5 minutes, after which the wire was given a ferrite/bainite structure by water cooling. Fig. 1 is a micrograph showing the different components (bainite, acicular ferrite and lamellar pearlite) of a microstructure obtained with steel grade 1, said microstructure comprising less than 35% acicular ferrite and less than 15% pearlite. Fig. 2 is a microscopic image showing the different compositions of the microstructure obtained with steel grade 3, which microstructure comprises 70% bainite and 30% acicular ferrite and lamellar pearlite.
The wire was then drawn at a cross-sectional reduction of 30% to obtain a round wire having a diameter of 12.54mm, and then cold-rolled at a thickness reduction of 50% to obtain a flat wire having a cross-section of 16mm × 6.3 mm. Herein, the total work hardening rate corresponding to the percentage reduction of the cross section at the end of the two cold operations was 57%. The wire was then subjected to stress relief annealing at a temperature of 600 ℃ for 30 seconds.
They were then tested to evaluate their use characteristics, the results of which are shown in table 2:
TABLE 2
NR: is not carried out
It goes without saying that the invention is not limited to the embodiments described above, but extends to numerous variants and equivalents.
The invention provides the following technical scheme:
scheme 1. a cold rolled steel wire characterized in that it has the following chemical composition, expressed in weight percentages:
0.2≤C%≤0.6
0.5≤Mn%≤1.0
0.1≤Si≤0.5%
0.2≤Cr≤1.0%
P≤0.020%
S≤0.015%
N≤0.010%
and optionally not more than 0.07% of Al, not more than 0.2% of Ni, not more than 0.1% of Mo and not more than 0.1% of Cu, the balance being iron and impurities inevitable as a result of processing, wherein the wire has a microstructure comprising bainite, and optionally up to 35% of acicular ferrite and up to 15% of pearlite.
Scheme 2. the cold rolled wire of scheme 1, comprising H exposed to a pH of 4.12No internal cracks appeared after 30 days of the environment for S.
Scheme 3. the cold-rolled wire according to scheme 1 or 2, which contains H2S and CO2Does not crack before two million bending cycles under alternating stress from +100MPa to +500 MPa.
Scheme 4. the cold rolled wire according to any one of schemes 1 to 3, having a mechanical tensile strength Rm of 900MPa to 1300 MPa.
Scheme 5. the cold rolled wire of any one of schemes 1 to 4, having a ductility a greater than or equal to 10%.
Scheme 6. a method of manufacturing a cold rolled wire according to any one of schemes 1 to 5, comprising the steps of:
-obtaining a hot-rolled steel wire rod having a diameter greater than or equal to 10mm,
-subjecting the wire rod to an austenitizing heat treatment at a temperature greater than 950 ℃ and then
-cooling the wire rod by austempering to a temperature of 350 ℃ to 600 ℃ to obtain a structure comprising at least 50% bainite and optionally up to 35% acicular ferrite and up to 15% pearlite, followed by completion of cooling to room temperature at a cooling rate of 30 ℃/s to 100 ℃/s,
-subjecting the cooled wire rod to a cold mechanical transformation operation with a total work hardening rate of 40% to 90% to obtain a mechanical tensile strength Rm of at least 800MPa, and then
-subjecting it to an optional stress relief heat treatment.
Scheme 7. the manufacturing method according to scheme 6, wherein the austenitizing heat treatment to which the wire rod is subjected is continuously performed on previously unwound wire in a gas furnace or in an induction furnace.
Scheme 8. the manufacturing method according to scheme 6 or 7, wherein the austenitizing heat treatment is performed for a time of 2 to 10 minutes.
Scheme 9. the manufacturing process according to any one of schemes 6 to 8, wherein the wire rod is cooled by isothermal quenching in a molten lead or salt based bath with an immersion time of 1 to 10 minutes followed by water cooling.
Scheme 10. the manufacturing method according to any of schemes 6 to 9, wherein the cold mechanical transformation operation comprises a drawing step followed by a cold rolling step, wherein the drawing is performed to obtain a cross-sectional reduction of at least 15%, the cold rolling is performed to obtain a thickness reduction of at least 30%.
Scheme 11. the manufacturing method according to any one of schemes 6 to 10, wherein the cold mechanical transformation operation is performed to obtain a mechanical tensile strength Rm of at least 1000MPa, followed by a stress relief heat treatment so that the mechanical tensile strength Rm is not reduced below 800 MPa.
Scheme 12. a flexible pipe for use in hydrocarbon extraction industry comprising at least one cold rolled wire according to any of the schemes 1 to 5 or obtained by the method according to any of the schemes 6 to 11.
Claims (10)
1. Cold rolled steel wire, characterized in that it has the following chemical composition, expressed in weight percentages:
0.2≤C%≤0.6
0.5≤Mn%≤1.0
0.1≤Si≤0.5%
0.2≤Cr≤1.0%
P≤0.020%
S≤0.015%
N≤0.007%
and which comprises not more than 0.07% of Al, not more than 0.2% of Ni, not more than 0.1% of Mo and not more than 0.1% of Cu, the remainder being iron and impurities inevitable as a result of processing, wherein the wire has a microstructure comprising bainite, and optionally up to 35% of acicular ferrite and up to 15% of pearlite, and being free of martensite; and is
Wherein the cold-rolled steel wire contains H2S and CO2Does not crack before two million bending cycles under an alternating stress of +100MPa to +500 MPa; and
the cold rolled steel wire has a mechanical tensile strength Rm of 900MPa to 1300 MPa.
2. The cold rolled steel wire according to claim 1, which contains H exposed to a pH of 4.12No internal cracks appeared after 30 days of the environment for S.
3. The cold rolled steel wire according to any one of claims 1 to 2, having a ductility a greater than or equal to 10%.
4. A method of manufacturing a cold rolled steel wire according to any one of claims 1 to 3, comprising the steps of:
-obtaining a hot-rolled steel wire rod having a diameter greater than or equal to 10mm,
-subjecting the wire rod to an austenitizing heat treatment at a temperature greater than 950 ℃ and then
-cooling the wire rod by austempering to a temperature of 350 ℃ to 600 ℃ to obtain a structure comprising at least 50% bainite and optionally up to 35% acicular ferrite and up to 15% pearlite, followed by completion of cooling to room temperature at a cooling rate of 30 ℃/s to 100 ℃/s, -subjecting the cooled wire rod to a cold mechanical transformation operation at a total work hardening rate of 40% to 90% to obtain a mechanical tensile strength of at least 800MPa, followed by
-subjecting it to an optional stress relief heat treatment.
5. The manufacturing method according to claim 4, wherein the austenitizing heat treatment to which the wire rod is subjected is continuously performed on a previously unwound wire in a gas furnace or in an induction furnace.
6. The manufacturing method according to claim 4 or 5, wherein the austenitizing heat treatment is performed for a time of 2 minutes to 10 minutes.
7. A manufacturing process according to any one of claims 4 to 5, wherein the wire rod is cooled by isothermal quenching in a molten lead or salt based bath with an immersion time of 1 to 10 minutes followed by water cooling.
8. A manufacturing process according to any one of claims 4 to 5, wherein the cold mechanical transformation operation comprises a drawing step followed by a cold rolling step, wherein the drawing is carried out so as to obtain a reduction in cross section of at least 15%, the cold rolling being carried out so as to obtain a reduction in thickness of at least 30%.
9. The manufacturing method according to any one of claims 4 to 5, wherein the cold mechanical transformation operation is performed to obtain a mechanical tensile strength Rm of at least 1000MPa, followed by a stress relief heat treatment so that the mechanical tensile strength Rm does not decrease below 800 MPa.
10. Flexible pipe for use in the hydrocarbon exploitation industry, comprising at least one cold-rolled steel wire according to any one of claims 1 to 3 or obtained by a method according to any one of claims 4 to 9.
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FRPCT/FR2013/000370 | 2013-12-24 | ||
PCT/FR2013/000370 WO2015097349A1 (en) | 2013-12-24 | 2013-12-24 | Cold-rolled wire made from steel having a high resistance to hydrogen embrittlement and fatigue and reinforcement for flexible pipes incorporating same |
CN201480070438.5A CN105849288A (en) | 2013-12-24 | 2014-12-22 | Cold-rolled steel wire having high resistance to hydrogen embrittlement and fatigue and reinforcement for flexible pipes incorporating same |
PCT/FR2014/000301 WO2015097354A1 (en) | 2013-12-24 | 2014-12-22 | Cold-rolled steel wire having high resistance to hydrogen embrittlement and fatigue and reinforcement for flexible pipes incorporating same |
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CN110724795A (en) * | 2019-09-30 | 2020-01-24 | 江苏冠晟超导科技有限公司 | Isothermal quenching heat treatment process of steel wire for wire |
CN111589893A (en) * | 2020-04-16 | 2020-08-28 | 江苏兴达钢帘线股份有限公司 | Steel wire for reinforcing rubber hose and production process thereof |
JPWO2022220281A1 (en) * | 2021-04-15 | 2022-10-20 | ||
WO2022220238A1 (en) * | 2021-04-15 | 2022-10-20 | 東京製綱株式会社 | Heat-treated steel material and heat treatment method for steel material |
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